Light-sensitive elements for color photography and process therefor



Sept. 6, WOO

W.. LIGHT-SENSITIVE ELEMENTS FOR COLOR PHOTOGRAPHY T HANSON, JR $271M 5123 AND PROCESS THEREFOR Filed Sept. 4. 1962 LI OH T-SBVS/ TI VE COLOR-FORMING LA YE R SILVER HAL/DE OPGAN/C SOLVENT CON TAIN/NG NO COUPLER BALLASTED COLOR-FORMING COUPLERW/TH SOLUB/L/Z/IVG 'GROUP ON COUPLING POSITION \JSUPPORT BLUE '5 ENSI TI VE LA YER CON 721ININ G m COLLOID SILVER HAL/DE EMULSION m A MOLECULAR DISPERSION 0F BALLASTED YELLOW- FORM/N 6 00 UPI. ER w/m COUPLING OFF SOLUBIL/ZI/IG OROu/g AND ORGANIC E ////-1 SOLVENT DISPERSION BLEA CHABLE YELLOW FILTER LA YER 20-\ GREEN-SENSITIVE LAYER CONTAINING COLLOID SILVER HAL/DE EMULSION MOLEcL/LAR DISPERSION 0F BALLASTED MAGENTA-FORMING COUPLER WITH COUPLING OFF SOLUB/L/ZING GROUP, AND ORGANIC SOLVENT DISPERSION SUPPORT iIJes Hey II '1 ZHIcOz mOOmQFZr:

I N V EN TOR.

ATTORNEY 6 AGENT 3,271,152 LIGHT-SENSITIVE ELEMENTS FOR COLOR PHOTOGRAPHY AND PROCES THEREFOR Wesley T. Hanson, .lr., Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Filed Sept. 4, 1962, Ser. No. 220,979 13 Claims. (Cl. 96-565) This invention relates to photographic silver halide emulsion layers that contain color-forming couplers, and in particular, to such layers containing couplers molecularly dispersed by water-solubilizing groups which are removed in processing to yield oil-soluble dyes which become dissolved in a high-boiling solvent emulsified in the layer.

Incorporated-coupler color photographic materials customarily use couplers which are made nonditfusing by the addition of hydrophobic ballast groups. One well known class of ballasted coupler is provided with sulfonic acid groups or similar strongly acidic groups in the molecule, to provide solubility in dilute alkaline solution and facilitate molecular dispersion in an aqueous hydrophilic colloid silver halide emulsion coating composition. This type of coupler is commonly referred to as a Fischer coupler and examples are disclosed in US. Patents Fischer 1,055,155, issued March 4, 1913; Fischer 1,102,028, issued June 30, 1914; and Wilmanns et al., 2,186,849, issued January 9, 1940.

Another well known method of incorporating ballasted couplers comprises dissolving them in high-boiling hydrophobic organic solvents and emulsifying this solution in very finely divided form in the hydrophilic colloid silver halide emulsion coating composition. This emulsion dispersion method is described, for example, in U.S. Patents Jelley et al., 2,322,027, issued June 15, 1943; Vittum et al.,

2,801,170, issued July 30, 1957; and Fierke et al., 2,801,-

i 171, issued July 30, 1957.

One disadvantage of the Fischer method of dispersion as practiced prior to my invention is the propensity of the resulting dye images to absorb light of a wider range of vwavelengths, i.e., to have a broad band instead of a desirable narrow, sharp absorption band.

While the coupler solvent dispersion method of dispersing ballasted couplers results in better color characteristics in the dye, there is sometimes an undesirable effect on stability because of the presence of residual coupler in highlight and middletone areas of the image. To a lesser degree the disadvantage of having the residual coupler in reactive association with the dye occurs also in the Fischer system. I have overcome this stability problem while retaining the improved dye characteristics of the coupler solvent dispersion system by providing a colloid silver halide composition which causes the image dye and residual coupler to be contained in separate phases in the for coating a photographic layer for the preparation of dye images, a dispersion of a high-boiling, hydrophobic, water-immiscible, organic solvent containing no coupler 3,27 l ,1152 Patented Sept. 6, '11 see W it and a separate aqueous solution of an alkali-soluble ballasted coupler compound which is insoluble in the organic solvent, but forms upon coupling with oxidized color developer during color development, image dyes that are hydrophobic and which are substantially all dissolved in the water-immiscible organic solvent.

Any of the high-boiling, water-immiscible solvents described in US. Patent 2,322,027, issued June 15, 1943, may be used. These solvents are low molecular weight, organic, crystalloidal materials having a boiling point above about C. which have a strong solvent action upon the dyes for-med by color development of my couplers but substantially no solvent action upon my hydrophilic couplers. Preferred solvents include di-n-butyl' phthalate, benzylphthalate, triphenyl phosphate, trio-ocresyl phosphate, diphenyl mono-p-tert-butylphenyl phosphate, monophenyl di-o-chlorophenyl phosphate, tri-ptert-butylphenyl phosphate, 2,4-di-n-amylphenol, etc.

The hydrophilic polymers useful in my invention as protective colloids, dispersants and film-formers, include gelatin and its water-soluble derivatives, polyvinyl alcohol, its water-soluble derivatives and copolymers, water-soluble vinyl polymers, such as polyacrylamide, imidized polyacrylamide, etc., and other water-soluble film-forming materials that form water-permeable coatings, such as colloidal albumin, water-soluble cellulose derivatives like ethanolamine cellulose acetate, etc. Compatible mixtures of two or more colloids can be used.

The couplers used to advantage according to my invention include those represented by the formula:

wherein C represents a coupler moiety, such as a phenol, a naphthol, a pyrazolone, or an open chain reactive methylene radical, e.g., a-benzoylacetanilide, etc., each of which has at least one ballasting group substituted on a noncoupling position on the coupler moiety, said ballasting group or groups having a total of at least 8 carbon atoms such that the ballasted coupler is substantially nondifiusing; and D is any removable water-solubilizing group which renders the ballasted coupler hydrophilic, said D group being attached to the coupler in the coupling position so that upon color development the solubilizing group is eliminated and the dye formed is nondiffusing, or alternatively, the pyrazolone and open chain active methylene couplers can also have the solubilizing group as part of an ester group attached to the carbon (normally the carbonyl carbon) of the coupler moiety that is adjacent to the coupling position. The solubilized ester group of these couplers hydrolyzes from the coupler in the alkaline color developer solution during color development and a nondiflusing hydrophobic dye is formed' The couplers of my invention are still further defined by the formulas for magenta couplers:

wherein R represents a hydrogen atom, an alkyl group, such as methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, tetradecyl, pentadecyl, heptadecyl, octadecyl, nonadecyl, docosyl, 2-chloroethyl, 2-bromobutyl, Z-hydroxypropyl, Z-phenylethyl, 2-(2,4,6-trichlorophenyl)ethyl, etc., an

3 aryl group, such as phenyl, 4-methylphenyl, 2,4,6-trichlorophenyl, 3,5-dibromophenyl, 4-trifiuoromethylphenyl, 2 trifluoromethylphenyl, 3 trifluoromethylphenyl, naphthyl, 2-chloronaphthyl, Z-ethylnaphthyl, etc., a heterocyclic group such as a thiazolyl, a benzothiazolyl, a naphthothiazolyl, an oxazolyl, a benzoxazolyl, a naphthoxazolyl, an imidazolyl, a benzimidazolyl, a naphthimidazolyl, a quino'linyl, a pyridyl, etc., R represents a hydrogen atom, an alkyl group, such as methyl, ethyl, 2- chloropropyl, 4-hydroxybutyl, octyl, pentadecyl, octadecyl, docosyl, phenylethyl, etc., an aryl group, such as phenyl, 2,4,6-trichlorophenyl, 4-methylphenyl, naphthyl, 2-chloronaphthyl, 4-ethylnaphthyl, etc., an amino group, such as amino, methylamino, diethylamino, phenylamino, Z-cyanophenylamino, 3-cyanophenylamino, 4-cyanophenylamino, Z-trifluoromethylphenylamino, 3-trifiuorornethylphenylamino, 4-trifluoromethylphenylamino, benzothiazolamino, etc., a carbonamido group, for example, an alkyl carbonamido group, such as ethylcarbonamido, butylcarbonamido, decylcarbonamido, phenethylcarbonamido, etc., an .arylcarbonamido group, such as phenylcarbonamido, 2,4,6-trichlorophenylcarbonamido, 4-methylphenylcarbonamido, 2-ethoxyphenylcarbonamido, naphthylcarbonamide, a :heterocyclic tcarbonamido, such as thiazolylcarbonamido, benzothiazolylcarbonamido, naphth-o thiazolylcarbonarnido, ox azolyloarbonamido, benzoxazolyl carbonarnido, imidazoly lcarbonamido, benzimidazo'lylcarbonamido, a sulfonamido group, for example, an alkylsulfonamiclo group, such as butylsulfonamido, dodecylsulfonamido, octadecylsulfonamido, docosylsulfonamido, phenylethylsulfonamido, etc., an arylsulfonamido, such as phenylsulfonamido, 2,4,6-trichlorophenylsulfonamido, Z-methoxyphenylsulfonamido, 4-methylphenylsulfonamido, naphthylsulfonamido, etc., a heterocyclic sulfonamido group, such as thiazolylsulfonamido, benzo thiazolylsulfonamido, oxazolylsulfonamido, benzoxazolylsulfonamido, imidazolylsulfonamido, benzimidazolylsulfonamido, pyridylsulfonamido, etc., an alkylsulfamyl group, such as propylsulfamyl, octylsulfamyl, pentadecylsulfamyl, octadecylsulfamyl, etc., an arylsulfamyl, such as phenylsulfamyl, 2,4,6 tribromophenylsulfamy], 2 methoXyphenyl-sulfamyl, naphthylsulfamyl, etc., a heterocylcie sulfamyl, such as a thiazolysulfamyl, a benzthiazolylsulfamyl, an oxazolylsulfamy], a benzimidazolylsulfamyl, a. pyridylsulfamyl group, etc., an alkylcarbamyl group, such as ethylcarbamyl, octylcarbamyl, pentadecylcarbamyl, octadecylcarbamyl, etc., arylcarbamyl, such as phenylcarbamyl, 2,4,6-trichlorophenylcarbamyl, etc., a heterocyclic carbamyl group, such as a thiazolylcarbamyl, a benzothiazolycarbarnyl, an oxazolylcarbamyl, an imid- 'azolylcarbamyl, a benzimidazolylcarbamyl group, etc.,

such that there are a total of at least 8 carbon atoms in either or both R and R of the coupler molecule; W represents a solubilizing group which makes the ballasted coupler hydrophilic, e.g., a solufonated arylthioether group,

.e.g., a 4-sulfophenylthio group, a sulfonated heterocyclic thioether group, such as a 2-(4-sulfobenzimidazolyl)-thio group, a 2-(S-sulfobenzothiazolyl)thio group, a 2-(6- sulfobenzoxazolyl)-thio group, a 4-sulfopyridylthio group, etc., a sulfonated phenylazo group, such as 4-sulfophenylazo, 2-sulfophenylazo, etc., the sulfo group of the above sulfo substituted groups includes the alkali metal (e.g., so dium, potassium, etc.) or organic ammonium (e.g., triethanolammonium, etc.) salt, a carboxylated aryl thioether group, e.g., a 3-carboxyphenylthio group, a carboxylated heterocyclic thioether group, such as a 2-(4-carboxybenzimidazolyDthio group, a 2-(6-carboxybenzothiazolyl)tl1io group, a 2-(5-carboxybenzoxazolyDthio group, a 4-carboxypyridylithio group, etc., a car-boxylalted phenyl group, such as 4-carboxyphenylazo, 2-carboxyphenylazo, etc., in which the carboxy group of the carboxy substituted groups described above includes the alkali metal (e.g., sclium, potassium, etc.) or organic ammonium (e.g., triethanol-ammonium, etc.) salt; W represents a sulfonated benzylidene group such as 4-sulfobenzylidene, 3-sulfob'enzylwherein R represents a carbamyl group, for example, an alkylcarbamyl in which the alkyl group is a group, such as methyl, ethyl, butyl, heXyl, octyl, dodecyl, pentadecyl, docosyl, 2-chlorobutyl, Z-hydroxyethyl, Z-phenylethyl, 2- (2,4,6 trichlorophenyDethyl, etc., a dialkylcarbamy'l group in which a combination of any two of the above alkyl groups are substituted on the N atom of the carbamyl group, an arylcarbamyl group in which the aryl group is a group, such as phenyl, 4-methylphenyl, 2,4,6- trichlorophenyl, 3,5-dibromophenyl, naphthyl, 3-ethylnaphthyl, etc., an alkyl arylcarbamyl group such as an N-methyl-N-phenyl carbamyl group, etc., a heterocyclic carbamyl group in which the heterocyclic group is a group such as a thiazolyl, a benzothiazolyl, a naphthiothiazolyl, an oxazolyl, a benzoxazolyl, a naphthoxazolyl, an imidazolyl, a benzimidazolyl, a naphthimidazolyl, a pyridyl, a quinolinyl, etc., a cyano group; R represents an alkyl group, such as methyl, 2-chloroethyl, 2-hydroxyethyl, Z-phenylethyl, butyl, tert-butyl, methoxy-dimethylmethyl, methoxy-diethylmethyl, methoxymethyldiethylmethyl, hexyl, pentadecyl, octadecyl, docosyl, 1,l-diethyloctadecyl, 2,4,6-trichlorophenylethyl, cyclohexyl, a terpenyl radical such as 7,7-dimethylnorbornyl, etc., an aryl group such as phenyl, 4-methylphenyl, 2,4,6-trichlorophenyl, 3,5-dibromophenyl, naphthyl, Z-chloronaphthyl, 3-ethylnaphthyl, etc., a heterocyclic group, such as a thiazolyl, a benzothiazolyl, a naphthothiazolyl, an OX- azolyl, a benzoxazolyl, a naphthoxazolyl, an imidazolyl, a benzimidazolyl, a naphthimidazolyl, a pyridyl, a benzofuranyl, and a quinolinyl group, such that there are a total of at least 8 carbon atoms in either or both the R and R groups in the coupler molecule; X is as defined previously; Y represents a solubilizing group, e.g., a sulfonated aryl thioether group, a sulfonated heterocyclic thioether group, a sulfonated phenylazo group, a sulfonated benzylidene group (including the alkali metal and organic ammonium salts of the sulfo moiety), a carboxylated aryl thioether group, a carboxylated heterocyclic thioether group, a carboxylated phenylazo group, and a carboxylated benzylidene group (including the alkali metal and organic ammonium salts of the carboxy moieties), all as described for W and W and in addition to these groups represents a sulfo group; and cyan dyeforming couplers represented by the formulas:

wherein 1 represents a phenolic or a naphtholic coupler moiety having any of the usual substituents, such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxy group, a halogen atom, etc., at least one ballasting group substituted on a noncoupling position of the coupler moiety, said ballasting group or groups having a total of at least 8 carbon atoms so the ballasted coupler is substantially nondiffusing; Z represents a solubilizing group which makes the coupler IX hydrophilic, such as a sulfonated aryl thioether group, sulfonated heterocyclic thioether group, a sulfonated phenylazo group (including the alkali metal and organic ammonium salts of the sulfo moiety), a carboxylated aryl thioether group, a carboxylated heterocyclic thioether group, a carboxylated phenylazo group (including the alkali metal and organic ammonium salts of the carboxy moieties), all as described for W and in addition represents a sulfo group, a carboxy group, a sulfoalkoxy group, such as 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutyoxy, 3- sulfobutoxy, etc., a carboxylalkoxy group, such as 2- carboxyethoxy, 3-carboxypropoxy, 4-carboxybutoxy, 3- carboxybutoxy, 4-carboxyamyloxy, etc. (including the alkali metal and organic ammonium salts of each of the sulfo and carboxy groups listed above); R and W are as defined previously; and n is an integer from 1 to 6.

Couplers illustrating those of Formulas V and IX include couplers, such as 1-hydroxy-3-carbethoxy-4-[4- (carboxymethyl)phenylazo] 4' (2,4-di-tert-amylphenoxy)-2-naphthanilide, 1| hydroxy 5-carbethoxy-4-[4- (carboxymethyl)phenylazo] 2' (2,4 di-tert-amylphenoxy)-2-naphthanilide, etc., of Tong US. Patent 2,772,- 163, issued November 27, 1956; l-hydroxy-4-sulfo-4-(N- methyl-N-octadecylamino)-2-naphthanilide, 1 hydroxy- 4-sulfo-4'-octadecyl-2-naphthanilide, etc., of Frohlich et al. US. Patent 2,357,395, issued September 5, 1944; lhydroxy-4-sulfo-N-octadecyl-2-naphthamide, oz benzoyloc-SUlfO-3-[3-(4 tert amylphenoxy)benzamido]acetanilide, etc. Any of the well known ballasted type couplers which are incorporated in photographic emulsions and which can be converted to the type coupler described, by adding a solubilizing group R, as defined above, only to a coupling off position, are used to advantage according to my invention after their conversion.

Compounds of Formulas IV and VIII are found in US. Patent 2,706,685, Salminen, issued Apnil 19, 1955, for example, l-phenyl-3-{ m-[a-2,4-di-(tert-amylphenoxy) acetamido]benzamido}- 5 m-sulfobenzoxypyrazole pyridinium salt.

In the practice of my invention, the azomethine or indoaniline dye is formed as a result of coupling between my hydrophilic Fischer coupler compounds and an organic amine color developing agent of the p-phenylenediamine type having at least one primary amino group, such as N,N- diethyl-aminoaniline which is oxidized during development. The dye formed has no water-solubilizing group and by virtue of the hydrophobic ballast group is readily soluble in the dispersed droplets of organic solvent. It dissolves in the solvent. As a result, the dissolved hydrophobic dye is separated by the interface between the liquid hydrophobic dispersed phase and the hydrophilic colloid continuous phase so that the likelihood of unwanted reaction between the coupler and the dye is very greatly reduced. In addition, the dye formed from Fischer couplers of the kind employed in my invention lacks ionic water-solubilizing groups and shows the improved color characteristics typical of azomethine image dyes dissolved in dispersed solvent.

My photographic elements are color developed to advantage with a color developer solution containing any of the well known primary aromatic amino silver halide developing agents, such as the p-phenylenediamines including the alkyl phenylenediamines and alkyl toluene diamines. These developing agents are usually used in the salt form such as the hydrochloride or sulfate which are more stable than the amine. The p-aminophenols and their substitution products may also be used where the amino group is unsubstituted. The N-alkyl sulfonamido alkyl-p-phenylenediamine agents of US. Patent 2,193,015 are also very useful. All of the developing agents have an unsubstituted amino group which enables the oxidation product of the developer to couple with the color-forming products that form a dye image. Included among the color developers are such typical illustrative examples as, 2-amino-5-diethylamino toluene hydrochloride, N ethyl B methanesulfonamidoethyl-3-methyl-4 aminoaniline sulfate, 4-arnino-N,N diethyl-3-methylaniline hydrochloride, 4 amino N-ethyl-N-(fi-methanesulfonamidoethyl)-m-toluidine sesquisulfate monohydrate, 3-methyl-p-aminodiethylaniline sulfate, 4-amino-N-ethyl- N-(fl-hydroxyethyl)aniline sulfate, N,N-dimethyl-p-phenylenediamine hydrochloride, etc.

In addition to the primary aromatic amino developing agent, the developer solution usually contains an alkaline material, such as an alkali metal carbonate or hydroxide, and may contain other well known addenda, such as an alkali metal sulfite, an alkali metal bisulfite, an alkali metal sulfate, an alkali metal bromide, an alkali metal iodide, etc., depending upon the specific requirements upon the developer solution.

Typical developing solutions that are used to advantage in processing my elements are illustrated by the following formulas:

N ethyl B-methanesulfonamido-ethyl-3-methyl-4- aminoaniline sulfate g 2.0 Sodium sulfite g 0.5 Sodium carbonate g 30.0 Water to l 1.0 4 amino N,N diethyl-3-methylaniline hydrochloride g 2.0 Sodium sulfite g 2.0 Sodium carbonate g 20.0 Potassium bromide --g 2.0 Water to l 1.0

My invention is illustrated but not restricted by the following examples.

EXAMPLE 1 Solution A.-0.5 gram of 1-hydroxy-4-sulfo-N-stearyl- Z-naphthamide was dissolved in 0.15 ml. of ethanol and 0.7 ml. of 20% aqueous solution of sodium hydroxide. This solution was added to 37 ml. of aqueous solution containing 1.5 g. of gelatin and 0.15 g. of Alkanol B, a propylated naphthalene sulfonate. The pH was then adjusted to 6.5.

Solution B.O.25 gram of di-n-butylphthalate, 22 ml. of 10% aqueous gelatin solution, 2 ml. of 5% Alkanol B solution and 10 ml. of water were mixed, passed through a colloid mill 5 times to disperse the di-n-butylphthalate.

Solution C.was prepared by dissolving 0.5 g. of lhydroxy-N-stearyl-2-naphthamide in 0.25 g. of di-n-butylphthalate and dispersing in 22 ml. of the gelatin-Alkanol B solution as described above for Solution B.

Solutions A and B were added slowly and successively with good agitation to 16 ml. of a medium speed silver bromoiodide emulsion and the mixture was coated on a suitably-subbed cellulose acetate support to a wet thickness of 0.006 inch and dried. This coating was designated Coating 1. Similarly, Solution A was added to 16 ml. of the same emulsion with agitation, coated on the same support to the same thickness, and dried. This was designated Coating 2. Coating 3 was prepared by adding Solution C to 16 ml. of the emulsion and coating and drying as with the other samples. The three coatings were exposed identically to an optical image and developed in a Z-amino-5-diethylaminotoluene developing composition to form negative silver and cyan dye image. The silver image and the residual silver halide were removed with a ferricyanide-hypo bleach leaving cyan negative images in the three coatings.

Table I compares the difference in maximum absorption of the three dye images and gives numerical data on the losses in density resulting from exposure in the Xenon Arc Fadeometer and in an oven at high humidity and also data on the printout and yellowing of the cou- "pler under Fadeometer and oven test conditions. The printout and yellowing were determined from the measured increases in density (in the areas of minimum density) caused by exposure to light, and exposure to heat and humidity respectively and are expressed in 8 solid formed. 31 grams of salt was added to the mixture, stirred, and filtered, and washed with 100 cc. of 30% salt solution.

The moist cake was ground with a mortar to a paste using 52 cc. of 30% salt solution, treated with 2 g. of anhydrous sodium acetate, washed again with brine and dissolved in 150 cc. of methanol and crystallized.

The material was filtered, washed with 25 ml. of methanol, and recrystallized from 80% acetic acid, yieldpercent reduction in light transmission. 10 ing 17 g. of product.

Table 1 Dye Coupler Coating Light Fade Heat Fade Percent Percent Am 30 Hours 1 Week Printout Ycllowing in m Xenon Arc 140F. Oven 30 Hours 1 Week Fadeorncter 75% R131. Xenon Arc 140 F. Oven Fadeometer 75% R H 1 In density units. 2 Reduction in transmission.

It is seen from Table 1 that the dye image in Coating 5 The intermediate 1-hydroxy-2-stearylnaphtharnide was 1 (i.e., the coating containing both the Fischer coupler prepared as follows: and the blank dispersion of the high-boiling, water-im- In a distilling flask g. (0.057 mole) of phenyl 1- miscible solvent) exhibits improved stability to both heat hydroxy-2-naphthoate and 15 g. (0.056 mole) of stearyland light as compared to the control Coating 2 (i.e., the amine were added and the mixture was heated in vacuo coating containing the Fischer coupler without the blank n to 150 C. for ten minutes, 3.2 g. of phenol being coldispersion of the high-boiling, water-immiscible solvent) 0 phenyl)-3-[ot-(3-pentadecylphenoxy)butyramido] S-pyrazolone. Coating 1 contained the water-soluble coupler and the solvent dispersion; Coating 2 contained the watersoluble coupler; and Coating 3 contained the solvent dispersion of the water-insoluble coupler.

Tables 2 gives the maximum absorption of the three 7 magenta dye images and gives numerical data on the losses in density resulting from exposure in the Xenon Arc Fadeometer.

Table 2 )unnx 0f the Dyo Light Fade of the Dye (in Coating in 111p. Density Units) Hours Xenon Arc Fadeometer The fog level was lowest and the contrast of Coating 1 was highest of the three coatings.

The preparations of the compounds of my invention described in the above examples are as follows:

(I) 1-}IYDROXY-4-SULFO-N-STEARYL-2NAPHTHAMIDE In a 200 cc. 3-necked flask, provided with a stirrer and thermometer was placed 78 cc. on concentrated H To the acid, while stirring, was added 13 g. (0.028 mole) of 1-hydroxy-2-stearylnaphthamide. The mixture was heated in a water bath to 80 C. (one hour), during which an amber solution formed. Heating was continued at 80-82 for 3.5 hours; then the solution was cooled externally to 35 C. and drowned in 260g. ice. A gray lected from the yellow solution. The residue solidified on cooling and was disolved in 300 ml. of methanol,

treated with charcoal powder, and filtered hot, yielding 15 g. of product, M.P. 86 C.

(II[) 1 2,4 DICHLORO 6 ME'II-IOXYPHENYL) 3 t (3 PENTADECYLPHENOXY)BUTYRAMIDO] 5- (3 -TSULI"OBENZOYLOXY)PYRAZOLE, PYRIDINIUM In a 2 liter Morton flask containing 500 ml. pyridine there was dissolved g. of 3-chlorosulfonyl benzoic acid (HOOCC H SO Cl). 69 grams of 1-(2,4-dichloro-6- methoxyphenyl) 3[cc (3 pentadecylphenoxy) butyramido]-5-pyrazolone (Weissberger et al., U.S. Serial No. 9,467, filed February 18, 1960, now U.S. Patent No. 3,062,653) was then added and the mixture was allowed to stand for 3 hours at room temperature. The resulting solution was poured into an ethylacetate-water mixture. The ethylacetate solution which separated was washed with water, 10% aqueous sodium bicarbonate solution, dilute hydrochloric acid, and dried over magnesium sulfate. The solution was evaporated to dryness, yielding 52 g. of product.

Although the examples show the use of elements with single color-forming layers, my color-forming layers are usually used in multilayer, multicolor photographic elements, such as are used in color photography. Such multicolor elements may have the diflferently sensitized layers arranged in any order on the support. For example, the red-sensitive cyan-forming layer may be the bottom layer coated over the support, the middle layer or the top layer with the blue-sensitive yellow-forming layer occupying one of the two remaining positions and the green-sensitive magenta-forming layer occupying the remaining position. Frequently, the cyan-forming layer is coated nearest the support with a magenta-forming layer and a yellow-forming layer, respectively, coated over the bottom layer. When the top layer is blue-sensitive, it is common practice to have a bleachable yellow filter layer between the top two sensitive layers. One or more of the layers may be false sensitized. It is preferable that all of the light-sensitive color-forming layers of my element be made according to my invention; however, it is possible to use a conventional layer for one or two of the three layers.

My invention is still further illustrated by the accompanying drawings, FIG. 1 and FIG. 2.

FIG. 1 is a cross-sectional view of one of my elements comprising support coated with light-sensitive colorforming layer 11 comprising colloid with dispersed silver halide grains 12, dispersed organic solvent 13 containing no coupler, and a molecular dispersion of 'ballasted colorforming coupler 14 with a solubilizing group in the coupling position.

FIG. 2 is a cross-sectional view of a typical multilayer, multicolor element comprising support 20, coated with red-sensitive layer 19 comprising a colloid silver halide emulsion intimately blended with a molecular dispersion of ballasted cyan-forming coupler with a coupling-off solu'bilizing group and a dispersion of organic solvent, green-sensitive layer 18 comprising a colloid silver halide emulsion intimately blended with a molecular dispersion of ballasted magenta-forming coupler with a couplingoff solubilizing group and a dispersion of organic solvent, bleachable yellow filter layer 17, and blue-sensitive layer 16 comprising a colloid-silver halide emulsion intimately blended with a molecular dispersion of ballasted yellowforming coupler with a coupling-off solubilizing group, and a dispersion of organic solvent.

My light-sensitive colored image'forming photographic elements are valuable for use in color photography. They are distinguished from other elements by having at least one and preferably three ditferently color-sensiized, colored-image-forming layers that are each comprised of a silver halide dispersion in a hydrophilic colloid that is intimately blended with a molecular dispersion of a ballasted color-forming coupler with a coupling off solubilizing group and a dispersion of an organic solvent containing no coupler. My elements are distinguished from elements now in use by having greatly reduced printout and yellowing of residual coupler and by having dyes of greatly improved stability to both heat and light.

The invention has been described in detail with particular reference to preferred embodiments thereof but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

I claim:

1. A light-sensitive photographic element comprising a support coated with at least one layer of an emulsion comprising a hydropholic colloid silver halide emulsion intimately blended with a dispersion of a color-forming coupler compound having a removable water-solubilizing group attached to said coupler on one of the positions, 1) a carbon atom in the coupling position and (2) a carbon atom adjacent to the carbon atom in the coupling position through a radical, and a hydrophobic ballasing group substituted on a noncoupling position of said coupler, and a dispersion of a coupler-free, hydrophobic, high-boiling, waterimmiscible crystalloidal organic solvent having a boiling point above about 175 C., said solvent having a strong solvent action on the dye formed upon color development of said color-forming coupler compound and having substantially no solvent action upon said color-forming coupler compound.

2. A light-sensitive photographic element comprising a support coated with at least one layer of an emulsion comprising a hydrophilic colloid silver halide emulsion intimately blended with (1) a dispersion of a color-forming coupler selected from the class consisting of those having the formulas:

I N=C-RR Ill 0 W wherein R represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group; R represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an aryl group, an amino group, a carbonamido group, a sulfonamido group, a sulfamyl group, and a carbamyl group, such that the total number of carbon atoms in the groups R and R is at least 8; R represents a member selected from the class consisting of a carbamyl group, and the cyano group; R represents a member selected from the class consisting of an alkyl group, an aryl group and a heterocyclic group, such that R and R together have at least a total of 8 carbon atoms; W represents a group selected from the class consisting of a sulfonated aryl thioether group, a sulfonated heterocyclic thioether group, a sulfonated phenylazo group, a carboxylated aryl thioether group, a carboxylated heterocyclic thioether group, a carboxylated phenylazo group; W represents a member selected from the class consisting of a sulfonated benzylidene group, a carboxylated benzylidene group; X represents a group selected from the class consisting of a sulfoalkyl group, a carboxyalkyl group, a sulfoaryl group, and a carboxyaryl group; Y represents a group selected from the class consisting of a sulfonated aryl thioether group, a sulfonated heterocyclic thioether group, a sulfonated phenylazo group, a sulfonated benzylidene group, a carboxylated aryl thioether group, a carboxylated phenylazo group, a carboxylated heterocyclic thioether group, a carboxylated benzylidene group, and a sulfo group; J represents a member selected from the class consisting of a phenolic coupler moiety and a naphtholic coupler moiety, said coupler moieties having at least one ballasting group substituted on a noncoupling position of the coupler, said ballasting groups having a total of at least 8 carbon atoms so the ballasted coupler is substan tially nondilfusing; and Z represents a group selected from the class consisting of a sulfonated aryl thioether group, a sulfonated heterocyclic thioether group, a sulfonated phenylazo group, a carboxylated aryl thioether group, a carboxylated heterocyclic thioether group, a carboxylated phenylazo group, a sulfo group, a carboxy group, a sulfoalkoxy group, and a carboxyalkoxy group; and V1 is an integer from 1 to 6; and (2) a dispersion of a coupler-free, hydrophobic, high-boiling, water-immiscible crystalloidal organic solvent having a boiling point above about 175 C., said solvent having a strong solvent action for the dyes formed upon color development of said color-forming coupler compound but having substantially no solvent action upon said color-forming coupler.

3. A light-sensitive photographic element of claim 2 in which the color-forming coupler is a pyrazolone coupler selected from those represented by Formula I of claim 2.

4. A light-sensitive photographic element of claim 2 in which the color-forming coupler is a pyrazolone coupler selected from those represented by Formula IV of claim 2.

5. A light-sensitive photographic element of claim 2 in which the color-forming coupler is an open chain coupler selected from those represented by Formula V of claim 2.

6. A light-sensitive photographic element of claim 2 in which the color-forming coupler is an open chain cou ler selected from those re resented by Formula VIII of claim 2.

7. A light-sensitive photographic element of Claim 2 in which the color-forming coupler is selected from those represented by Formula IX of claim it 8. A light-sensitive photographic element comprising a support coated with a layer comprising a gelatino silver halide emulsion blended intimately with (l) a dispersion of 1-hydroxy-4-sulfo-2-stearylnaphthamide, and (2) a dispersion of di-n-butylphthalate in gelatin.

9. A light-sensitive photographic element comprising a support coated with a layer comprising a gelatino silver halide emulsion blended intimately with (1) a dispersion of 1-hydroxy-4-sulfo-2-stearylnaphthamide, and (2) a phenoxy)butyramido] (3 sulfobenzoyloxy)pyrazole pyridinium salt, and (2) a dispersion of di-n-butylphthalate in gelatin.

10. A light-sensitive photographic element comprising a support coated with a layer comprising a gelatino silver halide emulsion blended intimately with (1) a dispersion of a-benzoyl-ot-sulfo-3[3 (4-t-amylphenoxy)benzamido] acetanilide, and (2) a dispersion of di-mbutylphthalate in gelatin.

11. A light-sensitive aqueous coating composition for coating light-sensitive layers on a photographic element, said composition comprising water, a hydrophilic colloid silver halide emulsion intimately blended with a dispersion of a color-forming coupler compound having a removable water-solubilizing group attached to said coupler on one of the positions, (1) a carbon atom in the coupling position and (2) a carbon atom adjacent to the carbon atom in the coupling position through a radical, and at least one hydrophobic ballasting group substituted on a noncoupling position of said coupler, and a dispersion of a coupler-free, hydrophobic, highboiling, water-immiscible icrystalloidal organic solvent having a boiling point above about 175 (3., said solvent having a strong solvent action on the dye formed upon color development of said color-forming coupler compound and having substantially no solvent action upon said color-forming coupler compound.

12. A process for forming a color image in a hydrophilic colloid silver halide emulsion layer comprising the steps of (1) imagewise conversion of a molecular dispersion of movable water-solubilizing group attached to said coupler on one of the positions (a) a carbon atom in the coupling position and (b) a carbon atom adjacent to the carbon atom in the coupling position through a radical, and a hydrophobic 'ballasting group substituted on a non-coupling position of said coupler, to a hydrophobic dye image by reaction with an imagewise distribution of an oxidized primary aromatic amine color developing agent and (2) solution of the said hydrophobic dye image in contiguous coupler-free hydrophobic high-boiling, water-immiscible organic solvent having a boiling point above about C., that is dispersed in the said layer so that substantially all of the said dye image is removed from reactive contact with the residual coupler which is insoluble in the said solvent and remains in the hydrophilic phase of the said emulsion layer.

13. In a color photographic process in which a light image-exposed hydrophilic colloid-silver halide emulsion containing a dispersed color-forming coupler is color developed by contacting with an aqueous, alkaline color developer solution containing a primary aromatic amine developing agent to produce a silver image and a dye image in light-exposed areas where the oxidized developing agent formed during reduction of light exposed silver halide to silver, couples with the said coupler present to produce the dye image, the improvement comprising the use of a color photographic element in which (a) the said coupler is a hydrophilic coupler having a removable water-solubilizing group attached thereto on one of the positions (1) a carbon atom in the coupling position and (2) a carbon atom adjacent to the carbon atom in the coupling position through a radical and a hydrophobic ballasting group substituted on a non-coupling position of said coupler, and (b) said hydrophilic colloid-silver halide emulsion contains a dispersion of a coupler-free hydrophobic, high-boiling, water-immiscible crystalloidal organic solvent having a boiling point above about 175 C., said solvent having a strong solvent action for the dye formed upon color developing of said color-forming coupler and having substantially no solvent action upon said color-forming coupler compound so that upon color development, the dye-image formed is hydrophobic and is substantially completely absorbed by the said coupler-free solvent dispersion thus separating the said dye image from reactive contact with residual coupler which remains in the hydrophilic phase of the said emulsion.

References Cited by the Examiner UNITED STATES PATENTS 2,357,395 9/1944 Frohlich et al 96-100 2,706,685 4/1955 Salminen 96-100 2,772,163 11/1956 Tong 9674 2,801,171 7/1957 Fierke et al. 96-l00 FOREIGN PATENTS 643,706 9/ 1950 Great Britain. 701,039 12/ 1953 Great Britain.

NORMAN G. TORCHIN, Primary Examiner. ABRAHAM H. WINKELSTEIN, Examiner. ,L T.- BROWN, Assistant Examiner.

PO-IWJ UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent 3,271,152 Dated September 6, I966 Inventor(s) W l y T. H nson, Jr.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 9, line L 5, delete the expression, "hydropholic", and substitute in its place --hydrophilic--; and line 55, delete th' expression "ballasing" and substitute in its place -ballasting- Column 11, line 37, delete the material, "'I -hydroxy-L sulfo-2- stearylnaphthamide, and (2) a phenoxy)", and substitute in its place, --1{2,L -dichloro--methoxyphenyl)-3F (3-pentadecylphenoXy)--.

SIGNED MID SEALED (SEAIJ Attest:

Edward MFletchfl', J WIILIAM E. eamnrm, m-

Attesting Officer C mmissioner of Patents 

12. A PROCESS FOR FORMING A COLOR IMAGE IN A HYDROPHILIC COLLOID SILVER HALIDE EMULSION LAYER COMPRISING THE STEPS OF (1) IMAGEWISE CONVERSION OF A MOLECULAR DISPERSION OF A NONDIFFUSING HYDROPHILIC COLOR FORMING COUPLER COMPOUND IN SAID LAYER, SAID COUPLER HAVING A REMOVABLE WATER-SOLUBILIZING GROUP ATTACHED TO SAID COUPLER ON ONE OF THE POSITIONS (A) A CARBON ATOM IM THE COUPLING POSITION AND (B) A CARBON ATOM ADJACENT TO THE CARBON ATOM IN THE COUPLING POSITION THROUGH A 